Application of dyestuffs



- thioglycollic acids carrying an anthraquinonyl Patented Apr. 7, 1936 7UNITED STATES PATENT OFFICE APPLICATION OF DY-ES'IUFFS Norman Chappell,Norman Hulton Haddock, and Frank Lodge, Blackley, England, assignors toImperial Chemical Industries Limited, a corporation of Great Britain NoDrawing. Application May 14,1934, Serial No. 725,652. In Great BritainMay 18, 1933 5 Claims.

applied compounds by treating with dilutemln eral acid at an elevatedtemperature.

The invention also comprises a process as in the preceding paragraph inwhich the o-aminophenylthioglycollic acids are applied from a bath whichis acidified by ammonium acetate, ammonium anthranilate, ammoniumphosphate, a mixture of ammonium sulphate and ammonia or anthranilicacid. Use of these acids in the dyebath permits addition of the whole ofthe acid to be used in the dyeing (as distinct from that used in thelactamization) to be added at the beginning of the dyeing operation andin general gives dyeings of greater fastness to rubbing.

Working according to our invention it is possible to obtain dyeings ofgreater fastness, especially fastness to potting and alkaline processes,and brightness than those described in the above mentionedspecification, and in general the fastness to potting and alkalineprocess on'wool is very good to excellent.

' We furtherdefine our o-aminoanthraqinonylsubstituent, as compounds ofthe constitution Aq-X-CaH-a s CHR c0111 where CsHa is the residue of aphenyl nucleus carrying as substitutents amino and thioglycollic acidgroups orthoto each other and an anthraquinonyl radical, represented byAq attached to a linking group X, and where R. stands for H, C'HaorC2H5, and X stands for a simple divalent radical derived from anauxochromic group such. as NH-, S, -NHCO, -CONH or NH-SO2, and WhereAq.may be further substituted by bromine or chlorine atoms or hydroxyl,alkoxyl, amino, alkylamino, acylamino, arylamino groups and the phenylresidue may be further substituted by bromine or chlorine atoms ormethyl groups. Further, one anthraquinonyl substituent may be shared bytwo o-aminophenylthioglycollic acid radicals.

These bodies may be prepared by the methods described in copending U. S.applications Ser. Nos. 682,728; 689,044; 702,416; 702,646 and 641,114.

The following examples in which parts are by weight are given toillustrate our invention, it

being understood that any of the compounds falling within the definitionof the products above given may be substituted for those used in thesespecific examples.

Example 1 The sodium salt of the acid of the constitution is applied towool in the following manner. 2 parts of the salt are dissolved in 2000parts of water at C. 50 parts of wet wool are added,

followed by 2 partsof ammonium acetate previously dissolved in water.The dyebath is maintained at -90", with gentle agitation for 1-1 hours..The wool is then rinsed in cold water and entered cold or luke-warmintoa solution of 3 parts of sulphuric acid in 2000 parts ofwater. Thetemperature is raised to 80 C., and kept at this 1 hour. The wool isremoved, rinsed in Water and treated with a solution of a mild.-detergent e. g. 4 parts of cetyl sodium sulphate in 2000 parts of Water,at 45 C. for about A hour to remove any traces of loosely adheringcolor. It is finally dried. The wool is dyed a very bright yellow shade,of excellent fastness to Washing, milling and potting. The fastness topotting is equivalent to that obtained with chrome colors and muchhigher than that generally obtained with acid colors.

Example 2 In the above. example, instead of using-2 parts of ammoniumacetate, a solution containing 2.5

parts of anthranilic'acid, neutralized with am- I monia, may besubstituted.

Example 3 lowed by 2 parts of ammonium acetate previously dissolvedinwater. tained 85-90", with gentle agitation, for .1-1 hours. The woolis then rinsed in cold water and entered cold or luke-warm into asolution oil-3 parts of sulphuric acid and 2 parts of cetyl pyridiniumbromide in 2000 parts of water. The

temperature is raised to C., and kept at this for A hour. The wool isremoved, rinsed in water, and treated with water to remove any traces ofadhering color. It is finally dried. The wool is dyed a verybright'yellow shade.

Example 4 The sodium salt of the acid of the constitution HlNQS nolomc cH: HN

NHCHI somoom is applied to wool in the following manner. 2 parts of thedye-stuff are dissolved in 2000 parts of water at80 C. and a solution of2 parts of the sodium salt of the formaldehyde-naphthalene sulphonicacid condensation product are added. 50' parts of Wet wool are added,followed by a solution of 2 parts of ammonium acetate. The dyebath ismaintained at -90" C., for 14% hours. The wool is rinsed in cold waterand entered warm or luke-warm into a solution of 3 parts of sulphuricacid in 2000 parts of water. The temperature is raised to 80 C. andmaintained at this for about 1 hour. The wool is rinsed in warm waterand treated with a mild detergent e. g. 4 parts of cetyl sodium sulphatein 2000parts 01 water at.45 C. for A hour to remove any trace ofadhering loose color. The wool is dyed a bright blue ofexcellent'fastness to washing, milling and potting.

Example. 5

The product used in Example 4 is applied to silk in the followingmanner. 1 /2 partsare dissolved in 2000 parts of water at 80 C-., 50parts of wet silk are added, followed by a solution of 2 parts ammoniumacetate. The dyebath is maintained at 85-90 C. for 1l hours. The fiberis rinsed in cold water and entered cold or lukewarm into a solution of3 parts of sulphuric acid -in 2000 parts of water. The temperature israised to 80 C., and maintained at this for about 1 hour. The fiber isrinsed in warm water and treated with a mild detergent, e. g. 4 parts ofcetyl sodium sulphate, in 2000 parts of water at 45 C. for PA hour toremove any trace of loosely adhering color. The silk is dyed a brightblue of good fastness to' washing.

Example 6 The sodium salt of the acid of the following constitution isapplied to wool in the following manner. 2 parts of dyestufliaredissol'ved in 2000 parts of The dyebath is mainwater at 80 C. and 50parts of wet wool added. 50 parts of 10% sodium sulphate solution areadded and the dyebath kept at -95 C. for 1 -2 hours. The wool isremoved-rinsed in cold water, or if desired a cold or lukewarm solutionof 4 parts of 'cetyl sodium sulphate in 2000parts or water, and immersedin a solution of 3 parts oi sulphuric acid in 2000 parts of water. Thetemperature is raised to 80-85" C. and kept at this for about 1 hour.The wool is rinsed with a solution of cetyl sodium sulphate as beforeand dried. It is dyed a bright blue of excellent fastness to light,washing, potting and milling.

Example 7 The sodium salt of the acid of constitution NHOH:

scnicoorr is applied to wool as follows. 2 parts of the dye-v stuff aredissolved in 2000 parts of water at 80 temperature is raised to 80 C.and kept at this for about 1 hour. The dyeing is rinsedein cold waterand dried. The shade is greenish blue and of excellent fastness tolight.

The shades obtainable from other dyestuffs are given in the followingtable:.

'80 B I 80- Dyestufl shade tamization s-omc o 0N8 NHGNH:

C0 Bluish- Green green 00 H NHQ-NH: s-cmcoona NH: O OONHQS'OHOOONSRcriidlisgi- Violet O NH: v

NH-CH:

co Reddish- Violet violet nn-sorQe-cmo'oom NH:

, NHCO- S-CH|COONa C0 NH! Qmnge- Yellow 0 0 yellow use 8 ac- Dyastuflshade tamization I 7 OH:

c o- O S'CHICOONB Bluish- Green Y NH omoo ONa 01H! NHcoQs-cH-o 00m 00NH, Orange Scarlet CHI NE NH: O00 s-ornoooNa Bluish- Green c 0 greenNH-QNH:

CHlCOONB.

C 0 Reddish- Violet blue NHQNH;

-oH,c OONa NH' 0 H:

oo Reddish- Bluishblue v violet NHCO' s-cmcoona NHzH: Us 0- c 0-Reddisb- Reddishblue blue NB: 0 o-Qs-on-coona NH: 7

NH-CH:

C 0 Bluish- Violet I violet QNH:

--ornoo 0N8 o 0 s s- 011,0 0 ONE Brown- Red c 0 on red Other dilutemineral acids such as hydrobromic, hydrochloric, nitric acids may beused for developing the color on the fiber in' place of the sulfuricacid specified in the specific examples.

We claim: I

1. In the process of dyeing textile fibers withanthraquinonyl-o-aminophenylthioglycollic acid dyestuffs of thefollowing formulav where CsH3 is the residue of a phenyl nucleuscarrying as substituents amino and thioglycollic acid groups ortho toeach other and an anthraquinonyl radical attached to a linking group X,and where R stands for H, CH3 or C2H5 and X stands for a radical of thegroup consisting of H, S, NHCO, CONH- or N.H.SO2-, and where Aq may befurther substituted by bromine or chlorine atoms or hydroxy, alkoxyl,amino, alkylamino, acylamino, arylamino groups and the phenyl residuemay be further substituted by bromine or chlorine atoms or methylgroups, the step which comprises applying the dyestuflf to the fiberfrom an aqueous solution containing a salt which under the conditions atwhich the dyeing is carried out will keep the solution continuallyacidified throughout the dyeing operation.

2. The process as defined in claim 1, wherein.

where CsHa is the residue of a phenyl nucleus carrying as substituentsamino and thioglycollic acid groups ortho to each other and ananthraquinonyl radical attached to a linking group X, and where R standsfor H, CH3 or C2H5, and X stands for a radical of the group consistingof NH, -S-, NHCO, -CONH- or NH.SO2, and where Aq may be furthersubstituted by bromine or chlorine atoms or hydroxyl, alkoxyl, amino,alkylamino, acylamino, arylamlno groups and the phenyl residue maybefurther substituted by bromine or chlorine atoms or methyl groups, anddeveloping the color on the fiber by heating in a dilute mineral acidsolution.

4. In the process of dyeing textile fibers withanthraquinonyl-o-aminophenylthioglycollic acid dyestuffs, the stepswhich comprise applying to the fiber from an aqueous solution keptcontinually acid throughout the dyeing operation, dyestuffs of theformula where Cal-Ia is the residue of a phenyl nucleus carrying assubstituents amino and thioglycollic acid groups ortho to each other andan anthravquinonyl radical attached to a linking group X,

tuted by bromine or chlorine atoms or hydroxyl, alkoxyl, amino,alkylamlno, acylamino, arylamlno groups and the phenyl residue may befurther substituted by bromine or chlorine atoms or methyl groups.

5. In the process of dyeing textile flberswithanthraquinonyl-o-amino'phenylthioglyco1lic acid dyestufls, the stepswhich comprise applying to the ilber from an aqueous solution keptcontinualcarrying as substituents amino and thioglycollic acid groupsortho to each other and an anthraquinonyl radical attached to a linkinggroup X, and where It stands for H, CH3, or C2H5-, and

x stands for a radical of the group consisting of 5 -NH--, --S--,'-NHCO, CONH or NH.SO2-, and where Aq may be further substituted bybromine or chlorine atoms or hydroxyl,

alkoxyl, amino, alkylamino, acylamino, arylamino 10 1y acid throughoutthe dyeing operation dyestuffs groups and the phenyl residue may befurther 10 of the formula substituted by bromine or chlorine atoms orNH, methyl groups and developing the color on the fiber by heating in a.dilute mineral acid solution. 15 3-03-4300 NORMAN CHAPPELL. is

t v NORMAN HULTON HADDOC'K.

where C13: is the residue 01' a phnyl nucleus v LODGE- CERTIFICATE orCORRECTION.

Patent No. 2,036,196. April 7, 19:56.

NORMAN CHAPPELL, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patentrequiring correction as follows: Page 1,first column, line 35, for "o-aminoanthraqinonyl-" read o-aminoanthraquin'onyh; page 2, first column, line 3, after the syllable "tained" insertthe word at; and page 5, second column, line 15, claim- 1 for "-H-"rea.cl-NH-; and hat the said Letters Patent should be read-with thesecorrections the'rein that the same may conform to the record of the casein the Patent Office.

1 S igned and sealed this 14th deyor July, A. D. 1936.

Henry Van Arsdale (Seal) Acting Commissioner of Patents;

i a l tuted by bromine or chlorine atoms or hydroxyl, alkoxyl, amino,alkylamlno, acylamino, arylamlno groups and the phenyl residue may befurther substituted by bromine or chlorine atoms or methyl groups.

5. In the process of dyeing textile flberswithanthraquinonyl-o-amino'phenylthioglyco1lic acid dyestufls, the stepswhich comprise applying to the ilber from an aqueous solution keptcontinualcarrying as substituents amino and thioglycollic acid groupsortho to each other and an anthraquinonyl radical attached to a linkinggroup X, and where It stands for H, CH3, or C2H5-, and

x stands for a radical of the group consisting of 5 -NH--, --S--,'-NHCO, CONH or NH.SO2-, and where Aq may be further substituted bybromine or chlorine atoms or hydroxyl,

alkoxyl, amino, alkylamino, acylamino, arylamino 10 1y acid throughoutthe dyeing operation dyestuffs groups and the phenyl residue may befurther 10 of the formula substituted by bromine or chlorine atoms orNH, methyl groups and developing the color on the fiber by heating in a.dilute mineral acid solution. 15 3-03-4300 NORMAN CHAPPELL. is

t v NORMAN HULTON HADDOC'K.

where C13: is the residue 01' a phnyl nucleus v LODGE- CERTIFICATE orCORRECTION.

Patent No. 2,036,196. April 7, 19:56.

NORMAN CHAPPELL, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patentrequiring correction as follows: Page 1,first column, line 35, for "o-aminoanthraqinonyl-" read o-aminoanthraquin'onyh; page 2, first column, line 3, after the syllable "tained" insertthe word at; and page 5, second column, line 15, claim- 1 for "-H-"rea.cl-NH-; and hat the said Letters Patent should be read-with thesecorrections the'rein that the same may conform to the record of the casein the Patent Office.

1 S igned and sealed this 14th deyor July, A. D. 1936.

Henry Van Arsdale (Seal) Acting Commissioner of Patents;

i a l

